US3592875A - Moulding compositions containing thermoplastic polyesters - Google Patents
Moulding compositions containing thermoplastic polyesters Download PDFInfo
- Publication number
- US3592875A US3592875A US804022A US3592875DA US3592875A US 3592875 A US3592875 A US 3592875A US 804022 A US804022 A US 804022A US 3592875D A US3592875D A US 3592875DA US 3592875 A US3592875 A US 3592875A
- Authority
- US
- United States
- Prior art keywords
- polyester
- polyesters
- weight
- tetrakis
- hydroxymethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229920000728 polyester Polymers 0.000 title abstract description 64
- 239000000203 mixture Substances 0.000 title description 22
- 238000000465 moulding Methods 0.000 title description 9
- 229920001169 thermoplastic Polymers 0.000 title description 2
- 239000004416 thermosoftening plastic Substances 0.000 title description 2
- -1 HYDROXYMETHYL GROUPS Chemical group 0.000 abstract description 15
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- 238000002347 injection Methods 0.000 abstract description 10
- 239000007924 injection Substances 0.000 abstract description 10
- 150000002009 diols Chemical class 0.000 abstract description 8
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical group C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 abstract description 4
- 150000001298 alcohols Chemical class 0.000 abstract description 4
- 150000001991 dicarboxylic acids Chemical class 0.000 abstract description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical group C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 11
- 230000008025 crystallization Effects 0.000 description 10
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 9
- 229920005862 polyol Polymers 0.000 description 9
- 150000003077 polyols Chemical class 0.000 description 9
- 238000001746 injection moulding Methods 0.000 description 7
- 238000006068 polycondensation reaction Methods 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- NIDZWWNRMZPMLN-UHFFFAOYSA-N [1,4,4-tris(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCC(CO)(CO)CC1 NIDZWWNRMZPMLN-UHFFFAOYSA-N 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 230000001737 promoting effect Effects 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000008187 granular material Substances 0.000 description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000155 melt Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- LCOOMOSZMKFHOC-UHFFFAOYSA-N 3,3,5,5-tetrakis(hydroxymethyl)oxan-4-ol Chemical compound OCC1(CO)COCC(CO)(CO)C1O LCOOMOSZMKFHOC-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- DHSSJEOOCSPBAC-UHFFFAOYSA-N [1,3,3-tris(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCC(CO)(CO)C1 DHSSJEOOCSPBAC-UHFFFAOYSA-N 0.000 description 3
- GEKVEPNTENNPEX-UHFFFAOYSA-N [3,5,5-tris(hydroxymethyl)oxan-3-yl]methanol Chemical compound OCC1(CO)COCC(CO)(CO)C1 GEKVEPNTENNPEX-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 3
- 125000004029 hydroxymethyl group Chemical group [H]OC([H])([H])* 0.000 description 3
- 239000002667 nucleating agent Substances 0.000 description 3
- 239000001993 wax Substances 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 description 2
- 235000011037 adipic acid Nutrition 0.000 description 2
- 239000001361 adipic acid Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000005690 diesters Chemical class 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 239000004415 thermoplastic moulding composition Substances 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- ICVIFRMLTBUBGF-UHFFFAOYSA-N 2,2,6,6-tetrakis(hydroxymethyl)cyclohexan-1-ol Chemical compound OCC1(CO)CCCC(CO)(CO)C1O ICVIFRMLTBUBGF-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- DZKUVVFEQHCDSK-UHFFFAOYSA-N P([O-])([O-])[O-].[Ge+3] Chemical compound P([O-])([O-])[O-].[Ge+3] DZKUVVFEQHCDSK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 125000006267 biphenyl group Chemical group 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- DMCTVRQBJMBEDT-UHFFFAOYSA-N phenol;1,1,1,2-tetrachloroethane Chemical compound ClCC(Cl)(Cl)Cl.OC1=CC=CC=C1 DMCTVRQBJMBEDT-UHFFFAOYSA-N 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-M terephthalate(1-) Chemical compound OC(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-M 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/16—Dicarboxylic acids and dihydroxy compounds
- C08G63/20—Polyesters having been prepared in the presence of compounds having one reactive group or more than two reactive groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
Definitions
- the present invention relates to moulding compositions containing thermoplastic polyesters which, when being processed by injection moulding, exhibit especially favorable properties.
- polyester moulding compositions are injected into heated moulds.
- inorganic substances that are insoluble in the polyester melt such as calcium carbonate, calcium sulfate or titanium dioxide and have a particle size of less than 2 microns, accelerate the crystallization of the polyester composition.
- the inorganic substances are added to the polyesters in an amount of from 0.05 to 0.5% by weight. The addition ensures that at a :suflicie'ntly high temperature of the mould the polyester reaches an optimum degree of crystallization during moulding so that alterations of shape and dimension after-crystallization are practically excluded.
- polyesters which are produced from terephthalic acid, ethylene glycol and an at least trihydric alcohol. Films made from polyesters of this type are still flexible and not crystalline after heating for one hour at 220 C.
- Moulded articles made from the polyester moulding compositions are predominantly used for industrial purposes, for example for the manufacture of gear wheels, pivot bearings and disk cams. They have to meet high standards with regard to their mechanical properties and, moreover, they should have an especially good surface quality, fill the mould completely, have a high dimensional stability and be free from flash formation.
- the surface properties of the moulded articles can be manipulated in various ways, by adding a lubricant, or suitably adjusting the injection conditions of the injection moulding machine. Although the conditions of injection moulding can be varied within very wide limits, it is very difficult to avoid flash formation with injection moulded polyethylene terephthalate.
- polyester obtained by polycondensation of (a) aromatic dicarboxylic acids and optionally small amounts of aliphatic dicarboxylic acids, and
- (b) saturated aliphatic or cycloaliphatic diols by a known method have especially favorable properties when the polycondensation is carried out in the presence of (c) alcohols containing more than 2 hydroxymethyl groups bound to a cyclohexane ring or a tetrahydropyran ring in an amount of from 0.01 to 2% by weight, preferably 0.03 to 0.5% by weight, calculated on the weight of the polyester.
- the polyesters produced in this manner have a reduced specific viscosity of from 0.6 to 2.4 dl./g., measured with a 1% solution in a 60:40 mixture of phenol and tetrachloroethane at 25 C.
- the polyesters obtained are especially suitable for injection moulding.
- Polyesters of the compositions specified above have not yet been described in literature. When injection moulded articles are made therefrom they are surprisingly free from flash formation. Moreover, the shaped articles made from the compositions of the invention have remarkably good mould release properties and excellent surface properties even with short dwell times.
- terephthalic acid is suitable in the first place.
- the polyesters may contain up to 5 mole percent of units of other aromatic or aliphatic dicarboxylic acids, for example isophthalic acid, diphenyl-4,4'-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid or adipic acid.
- ethylene glycol is especially suitable. It is likewise suitable, however, to use 1,4-bis-hydroxymethylcyclohexane. Besides ethylene glycol or 1,4- bis-hydroxymethyl-cyclohexlane, up to 10 mole percent of other aliphatic 'diols, for example 2,2-dimethyl-propane-diol-(l,3) or butane-diol-(l,4) may be contained in the polyester.
- the polyols may additionally contain a secondary hydroxyl group, such as, for example 2,2,6,6- tetrakis-hydroxymethyl-cyclohexanol-1 or tetrahydro-3, 3,5,5-tetrakis-(hydroxymethyl)-4-hydroxy pyran. Especially good results are obtained with 1,1,4,4-tetrakis-hydroxyrnethyl-cyclohexane.
- the polyols are used either individually or in admixture with one another.
- the polyesters are prepared in known manner, for example by reacting diesters of the dicarboxylic acids and low molecular weight aliphatic alcohols with the diol and the polyol.
- the polyol can be added at different stages of the manufacturing process of the polyester. It may be reacted With the diester of the dicarboxylic acid together with the diol.
- the polyol may be added to the reaction mixture after termination of the ester interchange reaction, whereupon the polyester is prepared by polycondensation in known manner.
- thermoplastic moulding compositions according to the invention contain polyesters having a reduced specific viscosity in the range of from 0.6 to 2.4 dl/g., preferably 1.0 to 1.7 dl/g., measured with 1% solutions in 60:40 mixtures of phenol and tetrachloroethane at 25 C.
- polyesters having high reduced specific viscosities the polyesters obtained by polycondensation in the melt are subjected to a post-condensation in the solid phase in known manner.
- the polyol-modified polyesters of the invention may also be components of thermoplastic moulding compositions containing besides the polyester, up to 20% by weight, preferably up to by weight of polymers, for example copolymers of ethylene and acrylic acid ester or of butadiene and styrene, which improve the impact strength of the polyesters.
- a crystallization promoting agent for example an inorganic nucleating agent such as kaolin, talc or an alkaline earth metal carbonate.
- the inorganic nucleating agents should preferably have a particle size below 2 microns.
- the polyester organic crystallization promoting agents for example ionic copolymers of ethylene and acrylic acid containing sodium ions as cations.
- the crystallization promoting substances can be incorporated into the polyester composition in various ways.
- the crystallization promoting agent and the polyester can be mixed, for example, by intensely stirring in the molten state. It is advantageous to mix as uniform as possible the granulated or powdered polyester with the powdery crystallization promoting substance, to melt the mixture in an extruder and to granulate it after cooling.
- the polyester moulding composition should contain as little moisture as possible, preferably at most 0.01% by weight.
- the granulated polyester moulding composition may be coated with an inert hydrophobic substance, for example a wax or paraffin.
- the temperature of the mould should be sufliciently above the second order transition temperature of the polyester.
- polyester moulding compositions on the basis of a modified polyethylene terephthalate mould temperatures in the range of from 120 to 150 C. are preferred.
- Polyethylene terephthalate (1) grams of phosphorous acid were added, the melt was again stirred for 15 minutes and 12.7 grams of germanium phosphite were added. During the course of 150 minutes the temperature of the melt was raised to 275 C. and the pressure was reduced to 0.2 mm. of mercury. The melt was stirred for 4 hours under these temperature and pressure conditions. A colorless polyester having a reduced specific viscosity of 0.88 dl/g., measured with a 1% solution in a :40 mixture of phenol and tetrachloroethane at 25 C., was obtained.
- the granulated polyester was dried for 5 hours at 180 C. under reduced pressure in an eccentric tumbling drier, subjected to rotation at room temperature together with 0.4% by weight of powdery aluminum silicate (47% SiO 38% A1 0 having a particle size of less than 2 microns), the mixture was homogenized in an extruder, granulated and then dried for 2 hours at C. under reduced pressure of 0.4 mm. of mercury in an eccentric tumbling drier.
- the granules were subjected to an aftercondensation in the solid phase.
- the after-condensed polyester had a reduced specific viscosity of 1.52 dl/g.
- the granules were coated with 0.2% by weight of polyethylene wax.
- Sheets of dimensions 60 x 60 X 2 mm. were injection moulded with the polyester composition at a temperature of the mould of 150 C.
- the sheets were injection moulded under different pressures, the pressures during dwell time being varied from 70 to 140 atmospheres gauge. In each case, the dwell time was 15 seconds. All sheets obtained were free from flash formation.
- EXAMPLES 2-3 Two modified polyethylene terephthalates were prepared as described in Example 1 containing (3) 0.113% by weight and (4) 0.057% by weight of 1,1,4,4-tetrakishydroxymethyl-cyclohexane. The polyesters were further treated as described in Example 1. The results obtained are summarized in the following table. Polyethylene terephthalate modified with 0.113% by weight of l,1,4,4- tetrakis-hydroxymethyl-cyclohexane could be injection moulded into sheets which were free from flash formation even under a pressure during dwell time of 140 atmospheres gauge. When the polyester contained only 0.057% by weight of 1,1,4,4-tetrakis-hydroxymethylcyclohexane flash formation could not be fully avoided under a pressure of atmospheres gauge.
- polyesters contained as nucleating agent 0.4% by weight of aluminum silicate powder (47% S102, 38% A1 0 75% of particles below 2 microns. The polyester granules were coated with 0.2% by Weight of polyethylene wax.
- polyester having a reduced specific viscosity of from 0.6 to 2.4 dl/g., measured with a 1% solution in a 60:40 mixture of phenol tetrachloroethane at C.
- thermoplastic molding composition containing, in addition to the polyester defined in claim 1, up to 20% by weight of a copolymer of ethylene and an acrylic acid ester or a copolymer of butadiene and styrene.
- a method of making a polyester which comprises polycondensing (a) terephthalic acid, (b) ethylene glycol or 1,4 bis hydroxene ethyl cyclohexane, and (c) 0.01 to 2% by weight of one or more polyols selected from the group consisting of 1,1,3,3 tetrakis hydroxymethylcyclohexane, tetrahydro 3,3,5,5 tetrakis hydroXymethyl pyran, 2,2,6,6 tetrakis hydroxymethyl cyclohexanol, tetrahydro 3,3,5,5 tetrakis hydroxymethyl- 4 hydroxy pyran and 1,1,4,4 tetrakis-hydroxymethylcyclohexane.
- component (a) contains up to 5 mole percent of an acid selected from the group consisting of isophthalic acid, diphenyl 4',4' dicarboxylic acid, naphthalene 2,6- dicarboxylic acid and adipic acid.
- component (b) is ethylene glycol
- component (b) is 1,4-bis-hydroxymethyl-cyclohexane.
- component (b) contains up to 10 mole percent of an aliphatic diol selected from the group of 2,2-dimethylpropanediol-( 1,3) and butane-diol-( 1,4)
- component (c) is a mixture of at least two polyols.
- a polyester as claimed in claim 1 having a reduced specific viscosity of from 1.0 to 1.7 dl/g.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyesters Or Polycarbonates (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19681770043 DE1770043A1 (de) | 1968-03-23 | 1968-03-23 | Thermoplastische Polyester enthaltende Formmassen |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3592875A true US3592875A (en) | 1971-07-13 |
Family
ID=5700373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US804022A Expired - Lifetime US3592875A (en) | 1968-03-23 | 1969-03-03 | Moulding compositions containing thermoplastic polyesters |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US3592875A (de) |
| AT (1) | AT288029B (de) |
| BE (1) | BE730333A (de) |
| CH (1) | CH510073A (de) |
| DE (1) | DE1770043A1 (de) |
| DK (1) | DK125479B (de) |
| ES (1) | ES364939A1 (de) |
| FR (1) | FR2004618A1 (de) |
| GB (1) | GB1248125A (de) |
| NL (1) | NL6903544A (de) |
| SE (1) | SE350059B (de) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894404A (en) * | 1988-09-19 | 1990-01-16 | Eastman Kodak Company | Molding compositions based on poly(1,4-cyclohexylene dimethylene terephthalate) containing an amide crystallization aid |
| US20040151854A1 (en) * | 2003-02-03 | 2004-08-05 | Pecorini Thomas Joseph | Extrusion blow molded articles |
| US20050070686A1 (en) * | 2001-07-18 | 2005-03-31 | Turner Sam Richard | Amorphous copolyesters |
| US20060229430A1 (en) * | 2001-07-18 | 2006-10-12 | Turner Sam R | Amorphous copolyesters |
| US20110074201A1 (en) * | 2008-04-08 | 2011-03-31 | Formway Furniture Limited | Injection moulding method |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011009766A1 (de) * | 2009-07-24 | 2011-01-27 | Basf Se | Hochfunktionelle, hoch- oder hyperverzweigte polyester sowie deren herstellung und verwendung |
-
1968
- 1968-03-23 DE DE19681770043 patent/DE1770043A1/de active Pending
-
1969
- 1969-02-18 DK DK89969AA patent/DK125479B/da unknown
- 1969-03-03 US US804022A patent/US3592875A/en not_active Expired - Lifetime
- 1969-03-07 NL NL6903544A patent/NL6903544A/xx unknown
- 1969-03-18 ES ES364939A patent/ES364939A1/es not_active Expired
- 1969-03-19 GB GB04372/69A patent/GB1248125A/en not_active Expired
- 1969-03-20 CH CH423369A patent/CH510073A/de not_active IP Right Cessation
- 1969-03-21 AT AT282669A patent/AT288029B/de not_active IP Right Cessation
- 1969-03-21 SE SE04003/69A patent/SE350059B/xx unknown
- 1969-03-24 FR FR6908553A patent/FR2004618A1/fr not_active Withdrawn
- 1969-03-24 BE BE730333D patent/BE730333A/xx unknown
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4894404A (en) * | 1988-09-19 | 1990-01-16 | Eastman Kodak Company | Molding compositions based on poly(1,4-cyclohexylene dimethylene terephthalate) containing an amide crystallization aid |
| US20050070686A1 (en) * | 2001-07-18 | 2005-03-31 | Turner Sam Richard | Amorphous copolyesters |
| US7026027B2 (en) | 2001-07-18 | 2006-04-11 | Eastman Chemical Company | Amorphous copolyesters |
| US20060229430A1 (en) * | 2001-07-18 | 2006-10-12 | Turner Sam R | Amorphous copolyesters |
| US7834127B2 (en) | 2001-07-18 | 2010-11-16 | Eastman Chemical Company | Amorphous copolyesters |
| US20040151854A1 (en) * | 2003-02-03 | 2004-08-05 | Pecorini Thomas Joseph | Extrusion blow molded articles |
| US20040180166A1 (en) * | 2003-02-03 | 2004-09-16 | Pecorini Thomas Joseph | Extrusion blow molded articles |
| US7025925B2 (en) | 2003-02-03 | 2006-04-11 | Eastman Chemical Company | Extrusion blow molded articles |
| US20110074201A1 (en) * | 2008-04-08 | 2011-03-31 | Formway Furniture Limited | Injection moulding method |
| US9003635B2 (en) * | 2008-04-08 | 2015-04-14 | Formway Furniture Limited | Injection moulding method |
Also Published As
| Publication number | Publication date |
|---|---|
| CH510073A (de) | 1971-07-15 |
| BE730333A (de) | 1969-09-24 |
| SE350059B (de) | 1972-10-16 |
| NL6903544A (de) | 1969-09-25 |
| DE1770043A1 (de) | 1971-09-23 |
| DK125479B (da) | 1973-02-26 |
| GB1248125A (en) | 1971-09-29 |
| AT288029B (de) | 1971-02-25 |
| ES364939A1 (es) | 1971-01-01 |
| FR2004618A1 (de) | 1969-11-28 |
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